Solvent effects on oxygen atom transfer reaction between manganese(V)-oxo corrole and alkene

Pseudo-first order reaction rate constants of 5,10,15-tris（pentafluorophenyl）corrole Mn（V）-oxo (F₁₅CMn（V）-oxo),5,15-bis（pentafluorophenyl）-10-（phenyl）corrole Mn（V）-oxo(F₁₀CMn（V）-oxo),5,15- bis（phenyl）-10-（pentafluorophenyl）corrole Mn（V）-oxo（F₅CMn（V）-oxo） and 5,10,15-tris（phenyl）corrole Mn（V）-oxo（F₀CMn（V）-oxo） with a series of alkene substrates in different solvents were determined by UV-vis spectroscopy.The results indicated that the oxygen atom transfer pathway between Mn（V）-oxo corrole and alkene is solvent-dependent.     

β-Octafluorinated tetrakis(ethoxycarbonyl)porphyrin

Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ).     

Numerical analysis of interaction between non-gray radiation and forced convection flow over a recess using the full-spectrum k-distribution method

In the present work, the interaction between non-gray radiation and forced convection in a laminar radiating gas flow over a recess including two backward and forward facing steps in a duct is investigated numerically. Distributions of absorption coefficients across the spectrum (50 cm^?1 < η < 20,000 cm^?1) are obtained from the HITRAN2008 database. The full-spectrum k-distribution method is used to account for non-gray radiation properties, while the gray radiation calculations are carried out using the Planck mean absorption coefficient. To find the divergence of radiative heat flux distribution, the radiative transfer equation is solved by the discrete ordinates method. The effects of radiation–conduction parameter, wall emissivity, scattering coefficient and recess length on heat transfer behaviors of the convection–radiation system are investigated for both gray and non-gray mediums. In addition, the results of gray medium are compared with non-gray results in order to judge if the differences between these two approaches are significant enough to justify the usage of non-gray models. Results show that for air mixture with 10 % CO₂ and 20 % H₂O, use of gray model for the radiative properties may cause significant errors and should be avoided.     

Stable-isotope dilution GC-MS method for ethanol in vapour ethanol and microdialysis systems based on carbonate-catalyzed extractive pentafluorobenzoylation

Common ethanol detection methods are not applicable to cell culture media and microdialysates due to interference with medium constituents including amino acids and pH indicators. We present a novel GC-MS method for the accurate and precise analysis of ethanol in cell cultures and microdialysates. The method is based on the carbonate-catalyzed extractive pentafluorobenzoylation of ethanol and deuterium-labelled ethanol serving as the internal standard and on their GC-MS analysis in the electron-capture negative-ion chemical ionization mode. The method was used to optimize experimental conditions in a custom-made ethanol vapour system utilized for studies examining ethanol influences on neuronal cell lines and in microdialysis.     

Unexpected one-pot synthesis of A3-type unsymmetrical porphyrin

The first direct synthesis of A₃-type unsymmetrical porphyrin is achieved via conventional pyrrole–aldehyde condensation in a one-pot procedure in an appreciable yield. Generalization of this approach to a variety of other aldehydes revealed that it is advantageous for highly electron-rich aldehydes giving unsymmetrical porphyrin, while electron-poor aldehydes even failed to cyclize under the same experimental conditions.     

Appended corrole manganese complexes:Catalysis and axial-ligand effect

A series of N-base appended corroles and their manganese complexes were synthesized and their binding constants with three different nitrogenous ligands, triethylamine, N-methylimidazole and pyridine, were evaluated by spectroscopy. Kinetic studies indicated that the presence of appended N- donor ligands may cause a significant enhancement of the rate of oxygen atom transfers （OAT） from （oxo）manganese（V） corrole to alkene, and the stronger axial ligand binding has impact on the rate of the oxidation reaction. Turnover frequency （TOF） for the catalytic oxidation of alkenes by appended manganese corroles varies with the following ligand order： acetamido 〈 pyridyl 〈 imidazolyl. The influence of the external axial ligands on the catalytic epoxidation was investigated by using appended acetamido manganese corrole as catalyst, with the results revealing that N-methylimidazole gave the best enhancement on the yields of total oxidation products among the investigated nitrogenous ligands.     

Theoretical analysis of porous radiant burners under 2-D radiation field using discrete ordinates method

This paper describes a theoretical study to investigate the heat transfer characteristics of porous radiant burners (PRBs). In the present work, a 2-D rectangular model is used to solve the governing equations for porous medium and gas flow before the premixed flame to the exhaust gas. The gas and the solid phases are considered in non-local thermal equilibrium and combustion in the porous medium is modeled by considering a non-uniform heat generation zone. The homogeneous porous media, in addition to its convective heat exchange with the gas, may absorb, emit and scatter thermal radiation. The radiation effect in the gas flow is neglected but the conductive heat transfer is taken into account. In order to analyze the thermal characteristics of porous burners, the coupled energy equations for the gas and porous medium in steady condition are solved numerically and the discrete ordinates method (DOM) is used to obtain the distribution of radiative heat flux in the porous media. Finally, the effects of various parameters on the performance of porous radiant burners are examined. The present results are compared with some reported theoretical and experimental results by other investigators and good agreement is found.     

Nanodiamond Decorated with Silver Nanoparticles as a Sensitive Film Modifier in a Jeweled Electrochemical Sensor: Application to Voltammetric Determination of Thioridazine

Nanodiamond? graphite (NDG) decorated with Ag nanoparticles (AgNPs‐NDG) was prepared and used to construct a novel sensitive sensor for the voltammetric determination of thioridazine (TR). The results indicate a remarkable increase in the oxidation peak currents together with a negative shift in the oxidation peak potentials, in comparison to the bare pyrolytic graphite electrode. Remarkable enhancement in microscopic area of the electrode along with strong adsorption of TR on the surface of the modified electrode resulted in a considerable increase in the peak current of TR. The surface morphology and the nature of the composite film deposited on PGE were characterized by scanning electron microscopy, atomic force microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Experimental variables, such as the deposited amount of the modifier suspension, pH of the supporting electrolyte, the accumulation potential and time are optimized by monitoring the CV responses of TR. Under the optimal conditions, the modified electrode showed a wide linear response to the concentration of TR in the range of 0.08–100 µM with a detection limit of 0.01 µM. The prepared modified electrode showed several advantages: simple preparation method, high stability and uniformity in the composite film, high sensitivity, long‐term stability and remarkable voltammetric reproducibility in response to TR. The modified electrode can be successfully applied for accurate determination of trace amounts of TR in pharmaceutical and clinical preparations.     

Numerical simulation of a three-layer porous heat exchanger considering lattice Boltzmann method simulation of fluid flow

Journal of Thermal Analysis and Calorimetry - The present study investigates the thermal characteristics of a proposed porous heat exchanger (PHE). This heat exchanger consists of three sections,...